EP0832083A1 - Microbicidal (mercapto-triazolyl methyl)-dioxacycloalkanes - Google Patents

Abstract

Novel mercapto triazolyl-dioxacycloalkanes of the formula (I) in which A is alkandiyl with 1 to 4 carbon atoms possibly substituted by halogen and/or alkyl with 2 or 3 carbon atoms, R is hydrogen or alkyl with 1 to 4 carbon atoms, X is halogen, alkyl with 1 to 4 carbon atoms, alcoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkyl halide with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy halide with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkylthio halide with 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl possibly substituted by halogen and/or alkyl with 1 to 4 carbon atoms or phenoxy possibly substituted by halogen and/or alkyl with 1 to 4 carbon atoms, and n is 0, 1, 2 or 3, and their acid addition salts and metal salt complexes, several process for the production of these substances and their use as microbicides in plant and material protection.

Description

Ml krobizide (Mercapto-tr1azolylmethyl) -d1oxacycloal kane

The present invention relates to new mercapto-triazolyl-dioxacycloalkanes, several processes for their preparation and their use as microbicides.

It has already become known that numerous azolyl-dioxacycloalkanes have fungicidal properties (cf. DE-A 2 551 560 and EP-A 0 065 485). So z. B. 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -2- (1,2,4-triazol-l-yl-methyl) -4-methyl-1,3-dioxolane and 2- Use (2,4-dichlorophenyl) -2- (l, 2,4-triazol-1-yl-methyl) -4-n-propyl-l, 3-dioxolane to combat fungi. The effectiveness of these substances is good, but leaves something to be desired in some cases at low application rates.

There have now been new mercapto-triazolyl-dioxacycloalkanes of the formula

in which

A represents, where appropriate, s alkanediyl having 2 or 3 carbon atoms substituted by halogen and / or alkyl having 1 to 4 carbon atoms,

R represents hydrogen or alkyl having 1 to 4 carbon atoms,

X represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 to 4 carbon atoms and 1 to 5 Halogen atoms, haloalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms or optionally substituted by Halogen and / or alkyl with 1 to 4 carbon atoms substituted phenoxy

and

n represents the numbers 0, 1, 2 or 3,

as well as their acid addition salts and metal salt complexes.

Those substances according to the invention in which the dioxacycloalkane ring is asymmetrically substituted contain one or optionally two chiral centers. The substances can therefore be obtained in the form of enantiomers or, if appropriate, also in the form of diastereomers. The present invention relates both to the individual isomers and to their mixtures.

It has also been found that mercapto-triazolyl-dioxacycloalkanes of the formula (I) and their acid addition salts and metal salt complexes are obtained if triazolyl-dioxacycloalkanes of the formula

in which

A, X and n have the meanings given above,

either

a) reacted successively with strong bases and sulfur in the presence of a diluent and then hydrolyzed with water, if appropriate in the presence of an acid,

or b) reacted with sulfur in the presence of a high-boiling diluent and, if appropriate, treated with water, if appropriate in the presence of an acid,

and optionally the compounds of the formula formed according to variants (a) and (b)

in which

A, X and n have the meanings given above,

with halogen compounds of the formula

R ¹ - shark (III)

in which

R ^{1 represents} alkyl having 1 to 4 carbon atoms and

Shark represents chlorine, bromine or iodine,

in the presence of an acid binder and in the presence of a diluent,

and optionally then adding an acid or a metal salt to the compounds of formula (I) thus obtained.

Finally, it was found that the new mercapto-triazolyl-dioxacycloalkanes of the formula (I) and their acid addition salts and metal salt complexes have very good microbicidal properties and can be used in a protective manner both in crop protection and in the material. Surprisingly, the substances according to the invention have a better microbicidal activity than the structurally most similar, known compounds of the same direction of action. The substances according to the invention thus exceed the 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -2- (1,2,4-triazol-l-yl-methyl) -4-methyl-1,3- dioxolane and 2- (2,4-dichlorophenyl) -2- (1,2,4-triazol-l-yl-methyl) -4-n-propyl-1,3-dioxolane with regard to the fungicidal properties.

The mercapto-triazolyl-dioxacycloalkanes according to the invention are generally defined by the formula (I).

A preferably represents alkanediyl which is optionally monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl and / or tert-butyl with 2 or 3 carbon atoms.

R preferably represents hydrogen, methyl or ethyl.

X preferably represents fluorine, chlorine, bromine, methyl, ethyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy,

Trifluoromethylthio, difluoromethoxy, optionally monosubstituted to trisubstituted, identically or differently by fluorine, chlorine and / or methyl substituted phenyl and / or for optionally monosubstituted to triple, identical or differently substituted by fluorine, chlorine and / or methylphenoxy.

n also preferably represents the numbers 0, 1, 2 or 3, where X represents the same or different radicals if n represents 2 or 3.

Preferred substances according to the invention are also addition products of acids and those mercapto-triazolyl-dioxacycloalkanes of the formula (I) in which A, R, X and n have those meanings which have been mentioned as preferred for these substituents and this index.

The acids that can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bi-functional carboxylic acids and hydroxycarboxylic acids, such as, for example Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid, or camphorsulfonic acid, saccharin and thiosaccharin.

In addition, preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and those mercapto-triazolyl-dioxacycloalkanes of the formula (I), in which A, R, X and n have the meanings which have been mentioned as preferred for these substituents and this index.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products. Particularly preferred such acids in this connection are the hydrogen halide acids, e.g. the hydrochloric acid and the bromine hydrogen acid, also phosphoric acid, nitric acid and sulfuric acid.

The mercapto-triazolyl-dioxacycloalkanes of the formula (I) in which R is hydrogen can be in the "mercapto" form of the formula

or in the tautomeric "thiono" form of the formula

available. For the sake of simplicity, only the "Mercapto" form is shown

The mercapto-triazolyl-dioxacycloalkanes listed in the following table may be mentioned as examples of substances according to the invention.

Table 1

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

If 2- (2,4-dichlorophenyl) -2- (1,2,4-triazol-l-yl-methyl) -4-n-propyl-1,3-dioxolane is used as starting material, n-butyl lithium as a strong base and sulfur powder as a reaction component, the course of the first stage, variant (a), of the process according to the invention can be illustrated by the following formula:

If 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -2- (l, 2,4-triazole-l -yl-methyl) -4-methyl-l, 3-dioxolane is used as the starting material, Sulfur powder as a reaction component and N-methyl-pyrrolidone as a diluent, the course of the first stage, variant (b), of the process according to the invention can be illustrated by the following formula:

sulfur

N-methyl pyrrolidone

If 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -2 - [(5-mercapto-1,2,4-triazol-l-yl) methyl] -4-methyl- 1,3-dioxolane as the starting material and methyl iodide as the reaction component, the course of the second stage of the process according to the invention can be illustrated by the following formula:

Formula (II) provides a general definition of the triazolyl-dioxacycloalkanes required as starting materials when carrying out the process according to the invention. In this formula, A, X and n preferably have those meanings which have already been mentioned as preferred for these radicals and this index in connection with the description of the substances of the formula (I) according to the invention. The triazolyl-dioxacycloalkanes of the formula (II) are known or can be prepared by known processes (cf. DE-A 2 551 560 and EP-A 0 065 485).

Suitable bases for carrying out the first stage of the process according to variant (a) according to the invention are all strong alkali metal bases customary for such reactions. Preferably used are n-butyl lithium,

Lithium diisopropylamide, sodium hydride, sodium amide and also potassium tert-butoxide in a mixture with tetramethylethylene diamine (= TMEDA).

When carrying out the first stage of the process according to variant (a) according to the invention, all inert organic solvents customary for such reactions can be considered as diluents. Are preferably usable

Ethers, such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane, furthermore liquid ammonia or also strongly polar solvents, such as dimethyl sulfoxide.

Sulfur is preferably used in the form of powder. For the hydrolysis, water, optionally in the presence of an acid, is used in carrying out the first stage of the process according to variant (a). In

All inorganic or organic acids customary for such reactions come into question here. Acetic acid, dilute sulfuric acid and dilute hydrochloric acid are preferably usable. However, it is also possible to carry out the hydrolysis with an aqueous ammonium chloride solution.

The reaction temperatures can be varied within a certain range when carrying out the first stage of the process according to variant (a). In general, temperatures between -70 ° C and + 20 ° C, preferably between -70 ° C and 0 ° C.

When carrying out all the steps of the process according to the invention, the procedure is generally under normal pressure. However, it is also possible to work under increased or reduced pressure. Working under increased pressure is particularly suitable when carrying out the first stage of the method according to variant (b).

When carrying out * the first step of the process according to the invention according to variant (a), 1 to 3 equivalents, preferably 1.0 to 2.5 equivalents, of more are generally employed per mole of triazolyl-dioxacycloalkane of the formula (II) Base and then an equivalent amount or an excess of sulfur. The reaction can be carried out under a protective gas atmosphere, for example under nitrogen or argon. Working up is carried out by customary methods. The reaction mixture is generally prepared using an in Extracted little soluble organic solvent water, the combined organic phases dried and concentrated and the remaining residue optionally purified by recrystallization and / or chromatography

When carrying out the first stage of the process according to variant (b) according to the invention, all the high-boiling organic solvents customary for such reactions can be used as diluents. Amides such as dimethylformamide and dimethylacetamide and heterocyclic compounds such as N-methylpyrrolidone are preferably usable. and also ethers such as diphenyl ether

Sulfur is also in the implementation of the first stage of the invention

Process according to variant (b) used in the form of powder After the reaction, a further treatment is optionally carried out, which is carried out in the same way as the hydrolysis when working according to variant (a)

The reaction temperatures can also be carried out within a relatively large range when carrying out the first stage of the process according to variant (b)

Range can be varied In general, temperatures between 150 ° C and 300 ° C, preferably between 180 ° C and 250 ° C.

When carrying out the first stage of the process according to the invention according to variant (b), 1 to 5 mol, preferably 1.5 to 3 mol, of sulfur are generally employed per mol of tπazolyl-dioxacycloalkane of the formula (II)

Working up is carried out by customary methods. In general, the reaction mixture is extracted with an organic solvent which is only slightly soluble in water, the combined organic phases are dried and concentrated, and the remaining residue, if appropriate, by customary methods such as recrystallization or chromatography existing

Free of impurities The compounds of the formula (Ia) required as starting substances when carrying out the second stage of the process according to the invention are substances according to the invention.

The halogen compounds required as reaction components in carrying out the process according to the invention in the second stage are indicated by

Formula (III) generally defined.

R ¹ preferably represents methyl or ethyl.

Shark also preferably represents chlorine, bromine or iodine.

The halogen compounds of the formula (III) are known.

Suitable acid binders for carrying out the second stage of the process according to the invention are all customary inorganic or organic bases. Alkaline earth metal or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetates such as

Sodium acetate, potassium acetate, calcium acetate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

Suitable diluents for carrying out the second stage of the process according to the invention are all inert organic solvents which are customary for such reactions. Ethers such as diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, furthermore nitriles such as acetonitrile and also strongly polar solvents such as dimethyl sulfoxide or dimethylformamide can preferably be used.

The reaction temperatures can be varied within a substantial range when carrying out the second stage of the process according to the invention. In general, temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C. When carrying out the second stage of the process according to the invention, 1 mol of mercapto-triazolyl-dioxacycloalkane of the formula (Ia), in general 1 to 2 mol of halogen compound of the formula (III) and an equivalent amount or an excess of acid binder are used Working up is carried out by customary methods. The procedure is generally such that aqueous base and a water-immiscible organic solvent are added to the reaction mixture, the organic phase is separated off, dried and concentrated. The product obtained can, if appropriate, be prepared by customary methods, for example by Recrystallization, freed from impurities still present

The mercapto-triazolyl-dioxacycloalkanes of the formula (I) obtainable by the process according to the invention can be converted into acid addition salts or metal salt complexes

For the preparation of acid addition salts of the compounds of formula (I), preference is given to those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention

The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the

Acid, for example hydrochloric acid, can be obtained and isolated in a known manner, for example by filtration, and, if appropriate, purified by washing with an inert organic solvent

For the preparation of metal salt complexes of the compounds of formula (I), preference is given to those salts of metals which are already in the

In connection with the description of the metal salt complexes according to the invention were mentioned as preferred metal salts

The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol and adding it to compounds of the

Formula (I) Metal salt complexes can be isolated in a known manner, for example by filtration, and, if appropriate, purified by recrystallization The active compounds according to the invention have a strong microbicidal action and can be used to protect against undesirable microorganisms, such as fungi and bacteria, in crop protection and in the material.

Fungicides are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes,

Basidiomycetes, Deuteromycetes.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as Xanthomonas oryzae;

Pseudomonas species, such as Pseudomonas lachrymans; Erwinia species, such as Erwinia amylovora; Pythium species, such as Pythium ultimum; Phytophthora species, such as Phytophthora infestans; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;

Plasmopara species, such as Plasmopara viticola; Peronospora species, such as Peronospora pisi or P. brassicae; Erysiphe species, such as Erysiphe graminis; Sphaerotheca species, such as Sphaerotheca fuliginea;

Podosphaera species, such as Podosphaera leucotricha; Venturia species, such as Venturia inaequalis; Pyrenophora species, such as Pyrenophora teres or P. graminea; (Coni form: Drechslera, Syn: Helminthosporium); Cochliobolus species, such as Cochliobolus sativus;

(Conidial form: Drechslera, Syn: Helminthosporium); Uromyces species, such as Uromyces appendiculatus; Puccinia species, such as Puccinia recondita; Tilletia species, such as Tilletia caries; Ustilago species, such as Ustilago nuda or Ustilago avenae;

Pellicularia species, such as Pellicularia sasakii; Pyricularia species, such as Pyricularia oryzae; Fusarium species, such as Fusarium culmorum; Botrytis species, such as Botrytis cinerea; Septoria species, such as Septoria nodorum; Leptosphaeria species, such as Leptosphaeria nodorum; Cercospora species, such as Cercospora canescens; Alternaria species, such as Alternaria brassicae; Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.

The active compounds according to the invention are particularly suitable for combating Pyricularia oryzae and Pellicularia sasakii on rice and for combating

Cereal diseases such as Pseudocercosporella, Erysiphe and Fusarium species. In addition, the substances according to the invention can be used very well against Venturia and Sphaerotheca. They also have a very good in-vitro effect.

In the protective material, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.

In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked by microorganisms or can be decomposed. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms. Within the scope of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.

Bacteria, fungi, yeasts, algae, for example, are microorganisms which can cause degradation or a change in the technical materials and called mucus organisms. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobansidium, such as Aureobansidium, such as Aureobansidium, such as Aureobansidium, such as Aureobansidium, such as Aureobansidium, such as Aureomansomaas like Trichoderma viride, Escherichia, like Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.

Depending on their respective physical and / or chemical properties, the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules,

Aerosols, ultra-fine encapsulations in polymeric substances and in coating compositions for

Seed, as well as ULV cold and warm mist formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate with

Use of surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents such as alcohols can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols , how Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; come in as emulsifying and / or foaming agents

Question: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; suitable dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

In the formulations, dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are used.

In crop protection, the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

When used in crop protection, the active compounds according to the invention can be used in the formulations in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, broaden the range of products or prevent the development of resistance. In some cases, synergistic effects also occur.

The following substances are suitable for the mixtures, for example.

Fungicides: 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4 ^l -trifluoromethyl-l, 3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylρhenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,

Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,

Cymoxanil, cyproconazole, cyprofuram,

Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxosolidone, edoloxazidololidolol, epidonolol, epidonolol, epidonolol, epidonol, epidonol, epidonol, epidonol

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futrianolide, Futrianol, Futin Furmecyclox,

Guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, I ibenconazole, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux-

Mixture,

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadarbox, Oxadoxcarbox Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozenes (PCNB) and sulfur

Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, Vinci Ozolin,

Zineb, ziram.

Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alpha-methrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,

Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin,

Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157

419, CGA 1 84699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin,

Clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,

Cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron,

Diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate,

Dimethylvinphos, dioxathione, disulfoton,

Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,

Ethoprophos, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothionx, Fhrionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon, Fufion, Fufion, Fufion, Fufion, Fufox, Fufox Heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, NI 25, Nitenpyram Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos,

Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, RH 5992,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin,

Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfön, Triflumuron, Trimethacarb, Vamidothetamin, Xamidothion, Xamidothion, Xamidothion.

A mixture with other known active ingredients, such as herbicides or with

Fertilizers and growth regulators are possible.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to prepare the active ingredient or the like Inject active ingredient into the soil yourself. The seeds of the plants can also be treated. In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the seed treatment, amounts of active ingredient are generally from 0.001 to

50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.

The means used to protect technical materials contain the

Active ingredients in general in an amount of 1 to 95%, preferably from 10 to 75%.

The application concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount of use can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The effectiveness and the spectrum of action of the active ingredients to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be produced therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or others are used Active ingredients to increase the spectrum of activity or to achieve special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

The preparation and use of the substances according to the invention can be seen from the following examples. Manufacturing examples

A mixture of 2.0 g (5 mmol) of 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -2- (1,2,4-triazol-l-yl-methyl) -4 -methyl-l, 3-dioxolane, 0.32 g (10 mmol) sulfur powder and

10 ml of absolute N-methylpyrrolidone is heated to 200 ° C. with stirring for 22 hours. The reaction mixture is then concentrated under reduced pressure (0.2 mbar). The remaining residue is mixed with ethyl acetate, and the resulting mixture is shaken out several times with saturated, aqueous ammonium chloride solution. The organic phase is over

Dried sodium sulfate and then concentrated under reduced pressure. The resulting crude product (1.8 g) is purified by chromatography on silica gel using a mixture of petroleum ether and ethyl acetate = 1: 1 as the eluent. In this way 0.9 g (41% of theory) of 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -2 - [(5-mercapto-1, 2.4 -triazol-1 -yl) -methyl] -4-methyl-1, 3-dioxolane in the form of a mixture of isomers.

MS (ci): 438 (M + Ff, 100%)

Examples of use

Example A

Erysiphe test (barley) / curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for curative effectiveness, young plants with spores of Erysiphe graminis f.sp. hordei pollinated. 48 hours after the inoculation, the plants are sprayed with the active compound preparation in the stated amount.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are shown in the following table.

Table A

Erysiphe test (barley) / curative

Active ingredient efficiency in%, based on the untreated control, with an active ingredient application rate of 125 g / ha

Known: 81

According to the invention: 100

(1-1)

Example B

Venturia test (apple) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, it is mixed

1 part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective efficacy, young plants are sprayed with the active ingredient preparation when dewy. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen Venturia inaequalis and then remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%.

Evaluation is carried out 12 days after the inoculation. 0% means one

Efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are shown in the following table.

Table B

Venturia test (apple) / protective

Active ingredient Efficiency in%, based on the untreated control, with an active ingredient concentration of 10 ppm

According to the invention: 100

(1-1)

Claims

Claims

1. Mercapto-triazolyl-dioxacycloalkanes of the formula

in which

A for optionally by halogen and / or alkyl with 1 to 4

Carbon atoms substituted alkanediyl having 2 or 3 carbon atoms,

R represents hydrogen or alkyl having 1 to 4 carbon atoms,

X represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,

Haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkylthio with 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms or represents phenoxy optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms

and

n represents the numbers 0, 1, 2 or 3,

as well as their acid addition salts and metal salt complexes.

2. mercapto-triazolyl-dioxacycloalkanes of formula (I) according to claim 1, in which A for alkanediyl which is optionally monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl and / or tert-butyl or 3 carbon atoms,

R represents hydrogen, methyl or ethyl,

X for fluorine, chlorine, bromine, methyl, ethyl, methoxy, methylthio,

Trichloromethyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,

Difluoromethoxy, optionally monosubstituted to trisubstituted, identical or different by fluorine, chlorine and / or methyl substituted phenyl and / or represents optionally monosubstituted to triple, identical or different by fluorine, chlorine and / or methyl substituted and

n stands for the numbers 0, 1, 2 or 3, where X stands for the same or different radicals if n stands for 2 or 3.

Process for the preparation of mercapto-triazolyl-dioxacycloalkanes

Formula (I) according to claim 1 and of its acid addition salts and metal salt complexes, characterized in that triazolyl-dioxacycloalkanes of the formula

in which

A, X and n have the meanings given above,

either

a) reacted successively with strong bases and sulfur in the presence of a diluent and then hydrolyzed with water, if appropriate in the presence of an acid, or

b) reacted with sulfur in the presence of a high-boiling diluent and if appropriate treated with water, if appropriate in the presence of an acid,

and optionally the compounds of the formula formed according to variants (a) and (b)

in which

A, X and n have the meanings given above,

with halogen compounds of the formula

R ¹ - shark (III)

in which

R ^{1 represents} alkyl having 1 to 4 carbon atoms and

Shark represents chlorine, bromine or iodine,

in the presence of an acid binder and in the presence of a

Reacting diluent,

and optionally then adding an acid or a metal salt to the compounds of formula (I) thus obtained.

4. Microbicidal agents, characterized by a content of at least one mercapto-triazolyl-dioxacycloalkane of the formula (I) according to claim 1 or on an acid addition salt or metal salt complex of a mercapto-triazolyl-dioxacycloalkane of the formula (I).

5. Use of mercapto-triazolyl-dioxacycloalkanes of the formula (I) according to Claim 1 or of their acid addition salts or metal salt complexes as microbicides in crop protection and in material protection.

6. A method for combating undesirable microorganisms in crop protection and in material protection, characterized in that mercapto-triazolyl-dioxacycloalkanes of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes on the microorganisms and / or their habitat deploys.

7. Process for the preparation of microbicidal agents, characterized in that mercapto-triazolyl-dioxacycloalkanes of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes are mixed with extenders and / or surface-active substances.